US20120164555A1 - Collector member, power generator, and method of manufacturing collector member for power generator - Google Patents

Collector member, power generator, and method of manufacturing collector member for power generator Download PDF

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Publication number
US20120164555A1
US20120164555A1 US13/417,893 US201213417893A US2012164555A1 US 20120164555 A1 US20120164555 A1 US 20120164555A1 US 201213417893 A US201213417893 A US 201213417893A US 2012164555 A1 US2012164555 A1 US 2012164555A1
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Prior art keywords
catalyst
catalyst layer
layer
collector member
carbon
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US13/417,893
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Inventor
Mutsuki Yamazaki
Yoshihiko Nakano
Wu Mei
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Toshiba Corp
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Toshiba Corp
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Assigned to KABUSHIKI KAISHA TOSHIBA reassignment KABUSHIKI KAISHA TOSHIBA ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: MEI, WU, NAKANO, YOSHIHIKO, YAMAZAKI, MUTSUKI
Publication of US20120164555A1 publication Critical patent/US20120164555A1/en
Priority to US14/515,245 priority Critical patent/US9972849B2/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/8605—Porous electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/88—Processes of manufacture
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • H01M4/8867—Vapour deposition
    • H01M4/8871—Sputtering
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/02—Details
    • H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
    • H01M8/023—Porous and characterised by the material
    • H01M8/0234—Carbonaceous material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1007—Fuel cells with solid electrolytes with both reactants being gaseous or vaporised
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to a collector member, a power generator using the collector member, and a method of manufacturing a collector member for a power generator.
  • Noble metals such as Pt are used as chemical catalysts instead of being used in accessories.
  • the noble metals are used in an exhaust emission control system of a vehicle and a solid polymer fuel cell, for example.
  • a methanol type solid polymer fuel cell using a methanol solution as a fuel can be operated at low temperature, and, at the same time, since the size and weight are small, the methanol type solid polymer fuel cell has been actively studied recently for the purpose of being applied to a power supply of a mobile apparatus and the like.
  • a catalyst synthesis method under vacuum using a sputtering method or an evaporation method is considered.
  • this method since a desired element can be directly evaporated to carbon of a supporting base material, reduction treatment is not required to be performed, and PtRu can be easily alloyed at room temperature.
  • catalyst fine particles can be supported only on carbon processed into a sheet (hereinafter referred to as “carbon paper”), and the thickness of a catalyst layer is approximately several ⁇ m.
  • carbon paper a sheet
  • the thickness of a catalyst layer is approximately several ⁇ m.
  • Methanol passed through the catalyst layer without being oxidized permeates a proton-conducting membrane separating an anode and a cathode to reach the cathode, and, thus, to generate water by the catalyst of the cathode.
  • the cathode When a large amount of water is generated in the cathode, the cathode is clogged with water, and the cathode cannot play an essential role, that is cannot decompose oxygen in the air and generate an oxygen radical, whereby the output is lowered.
  • the catalyst layer Although water is essential at an anode, if the catalyst layer is thin, the amount of water required for power generation cannot be held in the catalyst layer, so that a satisfactory performance may not be obtained. Thus, although it is considered to increase the thickness of the catalyst layer, if the thickness of the catalyst layer is to be increased, the catalyst layer becomes not fine particles but a film-like shape. Therefore, the surface area of the catalyst is small, and there is a problem that the power generation performance is reduced.
  • Patent Document 1 Japanese Patent Application National Publication (Laid-Open) No. 2007-515364
  • Patent Document 2 Japanese Patent Application Laid-Open (JP-A) No. 2006-147522
  • the present invention has been made in order to solve the above problems, and therefore has an object to provide a collector member having highly active catalyst particles or a catalyst layer and a high-performance power generator.
  • a further object of the present invention is to provide a method of manufacturing a collector member for a power generator that can manufacture the collector member.
  • a collector member comprising a sheet-shaped base material having a carbon-containing fiber and catalyst particles adhered to an outer periphery of the fiber, containing a noble metal or an alloy thereof, and having an average particle diameter of 0.1 to 2 ⁇ m.
  • a collector member comprising a first catalyst layer containing a noble metal or an alloy thereof, a second catalyst layer formed on the first catalyst layer and containing a noble metal or an alloy thereof, and a first intermediate layer interposed between the first catalyst layer and the second catalyst layer and containing a carbon fiber.
  • a power generator comprising the above collector member is provided.
  • a method of manufacturing a collector member for a power generator comprising growing a carbon fiber with a length shorter than a diameter of a carbon-containing fiber on an outer periphery of a sheet-shaped base material having the fiber and forming catalyst particles containing a noble metal or an alloy thereof on the outer periphery of the sheet-shaped base material by a physical vapor deposition method, using the carbon fibers as nuclei.
  • the collector member according to an aspect of the present invention the collector member according to another aspect, and the method of manufacturing a collector member for a power generator according to another aspect, a collector member having a highly active catalyst particles or catalyst layer can be provided. Further, according to the power generator according to another aspect of the present invention, a high-performance power generator can be provided.
  • FIG. 1 is a view showing a schematic configuration of a collector member according to a first embodiment
  • FIG. 2 is a SEM photograph of the collector member according to the first embodiment
  • FIG. 3 is a partially enlarged view of the collector member according to the first embodiment
  • FIG. 4 is a view schematically showing a manufacturing process of the collector member according to the first embodiment
  • FIG. 5 is a SEM photograph of a sheet-shaped base material formed with a carbon fiber according to the first embodiment
  • FIG. 6 is a schematic configuration diagram of a power generator according to the first embodiment
  • FIG. 7 is a SEM photograph of a collector member according to a reference example when a long carbon fiber is formed
  • FIG. 8 is a view showing a schematic configuration of a collector member according to a second embodiment
  • FIG. 9 is a view showing a schematic configuration of another collector member according to the second embodiment.
  • FIG. 10 is a graph showing a relationship between a thickness of a carbon fiber layer and an output voltage
  • FIG. 11 is a graph showing a relationship between a Nafion content percentage and an output voltage
  • FIG. 12 is a view schematically showing a manufacturing process of the collector member according to the second embodiment
  • FIG. 13 is a view schematically showing a manufacturing process of the collector member according to the second embodiment
  • FIG. 14 is a view schematically showing a manufacturing process of another collector member according to the second embodiment.
  • FIG. 15 is a view schematically showing a manufacturing process of another collector member according to the second embodiment.
  • FIG. 16 is a view schematically showing a manufacturing process of another collector member according to the second embodiment.
  • FIG. 17 is a graph showing a relationship between a thickness of a carbon fiber layer and a transfer efficiency
  • FIG. 18 is a schematic configuration diagram of a power generator according to the second embodiment.
  • FIG. 19 is a view showing a schematic configuration of a collector member according to a third embodiment.
  • FIG. 20 is a view showing a schematic configuration of a collector member according to a fourth embodiment
  • FIG. 21 is a SEM photograph showing a state of a catalyst when the catalyst is formed on a carbon paper by the conventional method.
  • FIG. 22 is a SEM photograph showing a state of a catalyst when the catalyst is formed on the carbon paper on which a long carbon fiber is grown by another conventional method.
  • FIG. 1 is a view showing a schematic configuration of a collector member according to the present embodiment.
  • FIG. 2 is a SEM photograph of the collector member according to the present embodiment.
  • FIG. 3 is a partially enlarged view of the collector member according to the present embodiment.
  • a collector member 10 comprises a sheet-shaped base material 11 having a carbon-containing fiber 11 a and catalyst particles 12 adhered to an outer periphery of the fiber 11 a.
  • the sheet-shaped base material 11 is not limited especially as long as it has a carbon-containing fiber.
  • Examples of the sheet-shaped base material 11 include a carbon paper.
  • an interval d between the fibers 11 a in the sheet-shaped base material 11 satisfies the condition of r/10 ⁇ d ⁇ r/3. This is because if the interval d is r/10 or more, the porosity is too high, and the crossover (the passing amount) of methanol becomes large to cause deterioration of performances. Meanwhile, if the interval d is r/3 or less, clogging easily occurs even if a slight amount of carbon nanofibers is grown.
  • the r and d can be determined by measuring the thickness of the fiber and an average value of intervals observed between the fibers at a plurality of points of a photograph observed by a scanning electron microscope (SEM) and calculating the average values of them.
  • SEM scanning electron microscope
  • the catalyst particles 12 are adhered to each other with no space therebetween so as to surround the outer peripheries of the fibers 11 a as shown in FIGS. 2 and 3 .
  • the catalyst particles 12 may have a multilayer structure including 25 catalyst layers, for example.
  • the catalyst particles 12 contain a noble metal or an alloy thereof.
  • the catalyst particles 12 contain a noble metal selected from the group consisting of gold (Au), silver (Ag), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt) or an alloy of them, and the catalyst particles containing a single Pt or an alloy of Pt and Ru is preferably used.
  • the catalyst particles 12 have an average particle diameter of 0.1 to 2 ⁇ m.
  • the average particle diameter is limited to this range because if the average particle diameter is less than 0.1 ⁇ m, there is a problem that the catalyst particles are easily burned when taken from a preparation apparatus.
  • a normal catalyst although nanosized noble metal fine particles are supported on a surface of a carbon powder, water, carbon dioxide, or the like is absorbed to suppress burning of the noble metal fine particles. If such a catalyst is placed into a vacuum device to remove absorbed water, and, thus, to take out the catalyst in the air, Pt fine particles of the catalyst decomposes oxygen in the air to generate a radical. The oxygen radical reacts with carbon as a carrier to be burned.
  • the fine particles are easily rapidly oxidized and therefore are burned.
  • a catalyst is prepared in a vacuum device as in the present invention, the above fireproof treatment cannot be performed, and therefore, if extremely fine particles are prepared, as soon as the fine particles are taken from an apparatus after the preparation to be exposed to the air, the fine particles are burned.
  • the average particle diameter is more than 2 ⁇ m, the particles are agglutinated with each other and become a film-like shape, and the surface area is reduced. “The average particle diameter” can be determined by measuring some points by a scanning electron microscope (SEM) and calculating the average value thereof.
  • the catalyst particles 12 contain a proton conductor (not shown) such as Nafion (trademark, manufactured by Du Pont) so that proton withdrawn from a fuel such as methanol by the catalyst easily reaches a proton-conducting membrane 26 to be described later.
  • a proton conductor such as Nafion (trademark, manufactured by Du Pont) so that proton withdrawn from a fuel such as methanol by the catalyst easily reaches a proton-conducting membrane 26 to be described later.
  • the gas permeability (P 1 ) of the collector member 10 is 50% or more of the gas permeability (P 2 ) of the single sheet-shaped base material 11 . Namely, it is preferable that P 1 ⁇ P 2 ⁇ 0.5. This is because if the gas permeability (P 1 ) of the collector member 10 is less than 50% of the gas permeability (P 2 ) of the single sheet-shaped base material 11 , the diffusion speed of the fuel is lowered, and supply is governed, so that the performance may be reduced.
  • the gas permeability can be measured by a mercury intrusion method.
  • the collector member 10 can be manufactured as follows, for example. First, the catalyst particles 12 are adhered to the outer periphery of the fiber 11 a constituting the sheet-shaped base material 11 by a sputtering method. Specifically, sputtering is performed in such a state that an Ar partial pressure is 0.5 Pa or more. Consequently, the catalyst particles 12 having an average particle diameter of 0.1 to 2 ⁇ m can be adhered to the outer periphery of the fiber 11 a.
  • the sheet-shaped base material 11 adhered with the catalyst particles 12 is immersed in a solution containing a proton conductor and then dried. Consequently, the collector member 10 can be manufactured.
  • FIG. 4 is a view schematically showing a manufacturing process of the collector member 10 according to the present embodiment.
  • FIG. 5 is a SEM photograph of a sheet-shaped base material formed with a carbon fiber according to the present embodiment.
  • carbon fibers 13 with a length shorter than a diameter of the fiber 11 a are grown on the outer periphery of the fiber 11 a constituting the sheet-shaped base material 11 by a low-pressure CVD method, for example.
  • the length of the carbon fiber 13 can be measured by observing a sample grown on a surface of the fiber 11 a with the SEM.
  • Examples of the carbon fiber 13 include a carbon nanofiber and a carbon nanotube.
  • the length of the carbon fiber 13 is not limited especially as long as it is shorter than the diameter of the fiber 11 a, the length is preferably approximately 1/10 to 1 ⁇ 2 of the diameter of the fiber 11 a, for example.
  • the catalyst particles 12 are formed on the outer periphery of the fiber 11 a by a physical vapor deposition method such as the sputtering method and a vacuum vapor deposition method, using the carbon fibers 13 as nuclei. Consequently, the catalyst particles 12 having an average particle diameter of 0.1 to 2 ⁇ m can be adhered to the outer periphery of the fiber 11 a.
  • the sheet-shaped base material 11 adhered with the catalyst particles 12 is immersed in a solution containing a proton conductor and then dried. Consequently, the collector member 10 can be manufactured.
  • FIG. 6 is a schematic configuration diagram of the power generator according to the present embodiment.
  • a power generator 20 functions as a fuel cell, and the power generator 20 comprises a membrane electrode assembly (MEA) 21 and separators 22 and 23 holding the membrane electrode assembly 21 therebetween.
  • MEA membrane electrode assembly
  • separators 22 and 23 holding the membrane electrode assembly 21 therebetween.
  • the power generator 20 is not limited thereto and may have a stack structure including a plurality of stacked single cells.
  • the separators 22 and 23 have flow paths 22 a and 23 a provided on plates formed of carbon, for example.
  • a fuel such as methanol and hydrogen is supplied into the flow path 22 a, and air is supplied into the flow path 23 a.
  • the membrane electrode assembly 21 is mainly constituted of an anode 24 , a cathode 25 , and a proton-conducting membrane 26 such as Nafion held by the anode 24 and the cathode 25 .
  • the anode 24 and the cathode 25 are constituted using the collector member 10 .
  • the catalyst particles 12 having an average particle diameter of 0.1 to 2 ⁇ m are adhered to the outer periphery of the fiber 11 a constituting the sheet-shaped base material 11 , and therefore, when converted into par unit weight, the active surface area as a catalyst is large in comparison with a film-shaped catalyst.
  • the catalyst particles 12 with high activity can be provided, and the power generator 20 with a high performance can be provided.
  • the adherence strength of the catalyst particles 12 to the sheet-shaped base material 11 is strong, the catalyst particles 12 are not easily dropped from the sheet-shaped base material 11 .
  • the carbon fiber 13 with a length shorter than the diameter of the fiber 11 a is used, and therefore, even when the carbon fibers 13 are grown on the outer periphery of the fiber 11 a, the gap can be maintained between the fibers 11 a as shown in FIG. 5 . Accordingly, the catalyst particles 12 can be intruded into the gap between the fibers 11 a, and therefore, even when the catalyst with the same amount as the carbon used when a long carbon fiber is used is adhered to the sheet-shaped base material by the sputtering method, a substantial evaporated surface area is larger than the case where the long carbon fiber is used. Thus, high power generation characteristics can be obtained.
  • FIG. 8 is a view showing a schematic configuration of a collector member according to the present embodiment.
  • FIG. 9 is a view showing a schematic configuration of another collector member according to the present embodiment.
  • a collector member 30 is mainly constituted of an anode 31 , a cathode 32 , and a proton-conducting membrane 33 held by the anode 31 and the cathode 32 .
  • the collector member 30 functions as a membrane electrode assembly.
  • the anode 31 is constituted of a first catalyst layer 34 , an intermediate layer 35 as a first intermediate layer, a second catalyst layer 36 , and a sheet-shaped base material 37 stacked in this order.
  • the intermediate layer 35 is interposed between the first catalyst layer 34 and the second catalyst layer 36 and contains the carbon fiber.
  • the first catalyst layer 34 is in contact with the proton-conducting membrane 33 . Since the sheet-shaped base material 37 is similar to the sheet-shaped base material 11 , the description will be omitted.
  • the first catalyst layer 34 and the second catalyst layer 36 are constituted of catalyst particles having an average particle diameter of 0.1 to 2 ⁇ m. This is because, as in the first embodiment, the active surface area as a catalyst is large in comparison with a film-shaped catalyst. Since the “average particle diameter” of the present embodiment is similar to the “average particle diameter” in the first embodiment, the description will be omitted.
  • the first catalyst layer 34 and the second catalyst layer 36 contain a noble metal or an alloy thereof.
  • the catalyst particles contain a noble metal selected from the group consisting of gold (Au), silver (Ag), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium (Ir), and platinum (Pt) or an alloy of them, and the catalyst particles containing an alloy of Pt and Ru is preferably used.
  • the first catalyst layer 34 and the second catalyst layer 36 may contain other elements than a noble metal or an alloy thereof.
  • aqueous methanol solution When an aqueous methanol solution is used as a fuel, the proper fuel concentration is different depending on a composition of metallic elements constituting a catalyst, and therefore, a composition of the first catalyst layer 34 and at least a portion of constituent elements of the second catalyst layer 36 or a composition ratio of the constituent elements may be different. Namely, for example, a catalyst using an alloy of Pt and Ru is suitable for a case where a fuel has a low methanol concentration and the supply amount is small.
  • multicomponent alloy catalyst containing, in an amount of approximately 10% to 50% in molar ratio to Pt, at least one or more kinds of elements selected from Hf, Ta, Fe, Mn, W, Mo, V, Al, Ni, and Si in addition to PtPu is suitable for a case where the methanol concentration is high.
  • the fuel diffusion speed can be suppressed by the intermediate layer 35 as described later. Namely, the fuel that is not used for power generation in the catalyst layer and permeates the catalyst layer can be suppressed.
  • the permeant fuel reacts at cathode to generate water, whereby the performance may be deteriorated. However, a high output can be obtained more stably by suppressing the permeant fuel.
  • the laminate structure comprising the first catalyst layer 34 , the intermediate layer 35 , and the second catalyst layer 36 is described; however, as shown in FIG. 9 , an intermediate layer 40 similar to the intermediate layer 35 is formed on the second catalyst layer 36 , and a third catalyst layer 41 may be formed on the intermediate layer 40 .
  • a third catalyst layer 41 may be formed on the intermediate layer 40 .
  • the molar ratio to Pt of at least one or more kinds of elements selected from Hf, Ta, Fe, Mn, W, Mo, V, Al, Ni, and Si may be different between the second catalyst layer 36 and the third catalyst layer 41 .
  • the first catalyst layer 34 may be constituted of a PtRu layer with a thickness of approximately 10 nm to 100 nm
  • the fuel diffusion speed is more strictly suppressed by the intermediate layer 35 and the intermediate layer 40 , and, at the same time, a concentration gradient of methanol can be easily controlled, so that a higher output can be obtained.
  • the first catalyst layer 34 and the second catalyst layer 36 contain a proton conductor in order to facilitate reaching of proton, withdrawn from methanol by the catalyst, to the proton-conducting membrane 33 .
  • the content (weight ratio) of the proton conductor to a metal functioning as a catalyst may be changed.
  • the “metal functioning as a catalyst” means that it includes all metals functioning as a catalyst but does not include metal oxides.
  • the content of the proton conductor of the first catalyst layer 34 is smaller than the content of the proton conductor of the second catalyst layer 36 , this is suitable for the case where a fuel with a high methanol concentration (mixed fuel of water and methanol) or pure methanol is used.
  • the proton content of the second catalyst layer 36 to which the fuel is supplied prior to the first catalyst layer 34 is high, the permeation rate (crossover) in the second catalyst layer 36 can be suppressed, the proton content of the first catalyst layer 34 may be small because the concentration or amount of the permeant fuel is reduced by being used in the power generation in the second catalyst layer 36 , and it is possible to obtain such an effect that water is easily returned in a passive type DMFC which returns water reacted at the cathode to the anode and generates electric power.
  • the content of the proton conductor of the first catalyst layer 34 is larger than the content of the proton conductor of the second catalyst layer 36 , this is suitable for an active type using a mixed fuel with a low methanol concentration containing a sufficient amount of water required for power generation. Namely, while the fuel permeating the second catalyst layer 36 is used in the power generation in the first catalyst layer 34 with a large content of the proton conductor, such an effect that can prevent the fuel from permeating the cathode can be obtained.
  • Examples of the carbon fiber constituting the intermediate layer 35 include a carbon nanofiber and a carbon nanotube.
  • the diameter of the carbon fiber constituting the intermediate layer 35 may be several nm to several ten nm.
  • FIG. 10 is a graph showing a relationship between a thickness of a carbon fiber layer and an output voltage when it is set that a current density of 150 mA/cm 2 is maintained. As shown in FIG. 10 , when the thickness of the carbon fiber layer is too large, fuel diffusion is inhibited, so that the performance as a fuel cell may be reduced.
  • the thickness of the intermediate layer 35 is preferably 100 nm or more and 30 ⁇ m.
  • the intermediate layer 35 preferably contains the proton conductor in order to impart a proton conductivity.
  • FIG. 11 is a graph showing a relationship between a Nafion content percentage of a carbon fiber layer and an output voltage when the thickness of the carbon fiber layer is 30 ⁇ m and it is set that a current density of 150 mA/cm 2 is maintained. As shown in FIG. 11 , if the content percentage of the proton conductor is too high, the fuel diffusion is inhibited, so that the performance may be reduced. Thus, it is preferable that the content percentage of the proton conductor is 1 wt. % or more and 40 wt. % or less with respect to the total of metal functioning as a catalyst and the proton conductor.
  • the thickness of the intermediate layer 35 When the thickness of the intermediate layer 35 is small, although the content of the proton conductor becomes small, the content percentage becomes high, so that the fuel diffusion can be easily inhibited. However, since the thickness of the intermediate layer 35 is small, it is allowable. Meanwhile, when the thickness of the intermediate layer 35 is large, although the content of the proton conductor is easily increased, the content percentage is not increased, and the content percentage acts effectively if it falls within the above range.
  • the cathode 32 is constituted of a catalyst layer 38 and a sheet-shaped base material 39 . Since the sheet-shaped base material 39 is similar to the sheet-shaped base material 11 , the description will be omitted.
  • the catalyst layer 38 is constituted of the catalyst particles having an average particle diameter of 0.1 to 2 ⁇ m. Since the materials of the catalyst layer 38 are similar to the materials of the first catalyst layer 34 , the description will be omitted.
  • FIGS. 12 and 13 are views schematically showing a manufacturing process of the collector member according to the present embodiment.
  • the first catalyst layer 34 is formed on the proton-conducting membrane 33 by a sputtering method in such a state that the Ar partial pressure is 0.5 Pa or more, for example.
  • the first catalyst layer 34 containing the catalyst particles having an average particle diameter of 0.1 to 2 ⁇ m can be obtained.
  • Ni (not shown) is sputtered on the first catalyst layer 34 , and the intermediate layer 35 is formed on the first catalyst layer 34 using Ni as the catalyst, as shown in FIG. 12B .
  • the intermediate layer 35 is formed by a low temperature process such as a low pressure CVD method, a plasma CVD method, and the sputtering method.
  • the laminate After the formation of the intermediate layer 35 on the first catalyst layer 34 , the laminate is immersed in a solution containing a proton conductor, whereby the intermediate layer 35 and the like contain the proton conductor. Then, after the laminate is dried, the second catalyst layer 36 is formed on the intermediate layer 35 by a physical vapor deposition method such as the sputtering method and a vacuum vapor deposition method, as shown in FIG. 12C .
  • the second catalyst layer 36 containing the catalyst particles having an average particle diameter of 0.1 to 2 ⁇ m can be obtained.
  • the laminate formed with the second catalyst layer 36 is immersed in the solution containing the proton conductor again, whereby the second catalyst layer 36 and the like contain the proton conductor. Thereafter, the laminate formed with the second catalyst layer 36 is dried. Subsequently, as shown in FIG. 13A , the sheet-shaped base material 37 is arranged on a surface of the second catalyst layer 36 , and they are heated and pressure-bonded. Consequently, the anode 31 is formed on the proton-conducting membrane 33 .
  • a catalyst layer 38 is formed on the surface opposite to the surface formed with the anode 31 in the proton-conducting membrane 33 by the sputtering method in such a state that the Ar partial pressure is 0.5 Pa or more, for example.
  • the catalyst layer 38 on the cathode side containing the catalyst particles having an average particle diameter of 0.1 to 2 ⁇ m can be obtained.
  • the sheet-shaped base material 39 is arranged on a surface of the catalyst layer 38 , and they are heated and pressure-bonded. Consequently, the cathode 32 is formed, and the collector member 30 is manufactured.
  • the collector member 30 can be manufactured as follows by utilizing a transfer technique.
  • FIGS. 14 to 16 are views schematically showing a manufacturing process of the collector member according to the present embodiment.
  • FIG. 17 is a graph showing a relationship between a thickness of a carbon fiber layer and a transfer efficiency.
  • a carbon fiber is grown on a substrate formed of carbon, preferably on a substrate 42 sintered with carbon by a low pressure CVD method or a plasma CVD method for example, and the intermediate layer 35 is formed.
  • FIG. 17 is the graph showing the relationship between the thickness of the carbon fiber layer and the transfer efficiency
  • the thickness of the intermediate layer 35 is preferably 100 nm or more and 10 ⁇ m or less.
  • the thickness of the intermediate layer 35 can be controlled by a C 2 H 4 flow rate, a substrate temperature, a pressure, a manufacturing time, and the like.
  • the condition of manufacturing the intermediate layer 35 with a thickness of 1 ⁇ m is exemplified as follows:
  • H 2 flow rate 250 SCCM
  • the first catalyst layer 34 is formed by the sputtering method in such a state that the Ar partial pressure is 0.5 Pa or more, for example, as shown in FIG. 14B .
  • the proton-conducting membrane 33 is arranged on a surface of the first catalyst layer 34 , and they are heated and pressure-bonded.
  • the substrate 42 is peeled from the laminate. Consequently, the first catalyst layer 34 and the intermediate layer 35 remain on the proton-conducting membrane 33 side, and the first catalyst layer 34 and the intermediate layer 35 are transferred. When the substrate 42 is peeled, the intermediate layer 35 is exposed.
  • the laminate After the substrate 42 is peeled, the laminate is immersed in a solution containing the proton conductor, whereby the intermediate layer 35 and the like contain the proton conductor. Subsequently, after the laminate is dried, the second catalyst layer 36 is formed on the intermediate layer 35 by a physical vapor deposition method such as the sputtering method and a vacuum vapor deposition method as shown in FIG. 15B .
  • the laminate formed with the second catalyst layer 36 is immersed in a solution containing the proton conductor again, whereby the second catalyst layer 36 and the like contain the proton conductor.
  • the sheet-shaped base material 37 is arranged on the surface of the second catalyst layer 36 , and they are heated and pressure-bonded. Consequently, the anode 31 is formed on the proton-conducting membrane 33 .
  • the second catalyst layer 36 is formed on the intermediate layer 35
  • the second catalyst layer 36 is previously formed on the sheet-shaped base material 37
  • the anode 31 may be formed by pressure-bonding the second catalyst layer 36 to the intermediate layer 35 .
  • the catalyst layer 38 is formed on the surface opposite to the surface formed with the anode 31 in the proton-conducting membrane 33 by the sputtering method in such a state that the Ar partial pressure is 0.5 Pa or more, for example.
  • the sheet-shaped base material 39 is arranged on the surface of the catalyst layer 38 , and they are heated and pressure-bonded. Consequently, the cathode 32 is formed, and the collector member 30 is manufactured.
  • FIG. 18 is a schematic configuration diagram of the power generator according to the present embodiment.
  • a power generator 50 functions as a fuel cell and comprises the collector member 30 and separators 51 and 52 holding the collector member 30 therebetween.
  • the power generator 50 is not limited thereto and may have a stack structure including a plurality of stacked single cells.
  • the separators 51 and 52 include flow paths 51 a and 52 a provided on plates formed of carbon, for example.
  • a fuel such as methanol and hydrogen is supplied into the flow path 51 a, and air is supplied into the flow path 52 a.
  • the intermediate layer 35 is interposed between the first catalyst layer 34 and the second catalyst layer 36 , the diffusion speed of a fuel such as methanol can be controlled by the intermediate layer 35 . Consequently, the fuel permeating the cathode 32 can be significantly reduced. Further, water required for power generation can be held properly.
  • the active surface area as a catalyst is large in comparison with a film-shaped catalyst. Consequently, highly active catalyst particles can be provided, and the power generator 50 with a high performance can be provided.
  • a catalyst layer is formed by the physical vapor deposition method such as the sputtering method
  • the catalyst particles are localized, and the density is high. Namely, when a cross section of the catalyst layer in a through-layer direction is observed, there is a layer in which the catalyst particles are localized, and in the layer with the localized catalyst particles the density of the catalyst is higher than other portions of the catalyst layer. Consequently, the reaction efficiency is high, and a high performance can be obtained by a small amount of catalyst.
  • this premises overcoming such a problem that unreacted methanol easily goes to the cathode.
  • the fuel permeating the cathode 32 can be significantly reduced by the intermediate layer 35 , a high performance can be obtained with a small amount of catalyst. Particularly when an amount of fuel is large, a high output can be obtained.
  • FIG. 19 is a view showing a schematic configuration of a collector member according to the present embodiment.
  • the thickness of a first catalyst layer 34 and the thickness of a second catalyst layer 36 are different from each other. Specifically, in FIG. 19 , the thickness of the second catalyst layer 36 is larger than the thickness of the first catalyst layer 34 .
  • the thickness of the first catalyst layer 34 and the thickness of the second catalyst layer 36 are different from each other, an effect similar to that when the concentration of the proton conductor is different can be obtained. Namely, this is suitable for the case where a fuel with a high methanol concentration (mixed fuel of water and methanol) or pure methanol is used.
  • the thickness of the first catalyst layer 34 may be small because the concentration or amount of the permeant fuel is reduced since the fuel is used in the power generation in the second catalyst layer 36 , and it is possible to obtain such an effect that water is easily returned in a passive type DMFC which returns water reacted at the cathode to the anode and generates electric power.
  • the thickness of the first catalyst layer 34 is larger than the thickness of the second catalyst layer 36 , this is suitable for an active type using a mixed fuel with a low methanol concentration containing a sufficient amount of water required for power generation. Namely, while the fuel transmitted through the second catalyst layer 36 is used in the power generation in the first catalyst layer 34 with a large thickness, such an effect that can prevent the fuel from permeating the cathode can be obtained.
  • FIG. 20 is a view showing a schematic configuration of a collector member according to the present embodiment.
  • an intermediate layer 60 as a second intermediate layer is formed between an intermediate layer 35 and a second catalyst layer 36 .
  • the intermediate layer 60 is constituted of a proton conductor and carbon. Namely, the intermediate layer 60 does not contain element to be a catalyst.
  • the second catalyst layer 36 can be suppressed from being covered by water.
  • PtRu was sputtered on a carbon paper having a carbon fiber as a sheet-shaped base material, for example on TGH-090 manufactured by Toray Industries, Inc. under the following conditions so that the thickness was approximately 0.3 mg/cm 2 per a unit area of a carbon fiber.
  • PtRu particles formed under the condition have an average particle diameter of 0.1 to 2 ⁇ m and were adhered to the outer periphery of the carbon fiber constituting the carbon paper.
  • the condition was as follows:
  • Ar flow rate 50 SCCM
  • SCCM is a unit representing a flow rate (ml/min) in terms of a normal state (0° C., 1 atmosphere).
  • the sample obtained as described above was immersed in a solution prepared by dissolving Nafion in ethanol to have a concentration of 2 wt. % and then dried at a room temperature, and an anode and a cathode as collector members were manufactured.
  • Nafion 117 manufactured by Du Pont as a proton conductive membrane was held between the anode and the cathode and heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and a membrane electrode assembly was manufactured.
  • a Ni layer with a thickness of approximately 20 nm was formed on a carbon paper having a carbon fiber as a sheet-shaped base material by a sputtering method. Subsequently, the carbon paper formed with the Ni layer was placed for 5 minutes under the following condition, and a minute carbon fiber was grown on an outer periphery of a fiber constituting the carbon paper, by a low pressure CVD method, using Ni as a nucleus. The length of the grown carbon fiber was approximately 1/10 to 1 ⁇ 2 of the diameter of the carbon fiber of the carbon paper.
  • the condition was as follows:
  • H 2 flow rate 200 SCCM
  • PtRu was sputtered on the carbon paper with the grown carbon fiber under the following conditions so that the thickness was approximately 0.3 mg/cm 2 .
  • PtRu particles formed on the carbon fiber had an average particle diameter of 0.1 to 2 ⁇ m and were adhered to the outer periphery of the fiber constituting the carbon paper in a state of using the carbon fibers as nuclei. The condition was as follows:
  • Ar flow rate 50 SCCM
  • the sample obtained as described above was immersed in a solution prepared by dissolving Nafion in ethanol to have a concentration of 2 wt. % and then dried at a room temperature, and an anode and a cathode as collector members were manufactured.
  • Nafion 117 manufactured by Du Pont as a proton conductive membrane was held between the anode and the cathode and heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and a membrane electrode assembly was manufactured.
  • PtRu was sputtered on the Nafion 117 (manufactured by Du Pont) as a proton conductive membrane under the following condition to form a PtRu layer with a thickness of 200 nm as a first catalyst layer.
  • the PtRu layer formed under the condition was constituted of PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • a Ni layer with a thickness of 50 nm was formed on the PtRu layer by a sputtering method under a similar condition.
  • the condition was as follows:
  • Ar flow rate 50 SCCM
  • H 2 flow rate 250 SCCM
  • the sample obtained as described above was immersed in a solution prepared by dissolving Nafion in ethanol to have a concentration of 2 wt. %.
  • the sample was dried at a room temperature, and thereafter, a PtRu layer with a thickness of 200 nm was formed as a second catalyst layer on the carbon fiber layer by the sputtering method.
  • the PtRu layer formed on the carbon fiber layer was constituted of PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • the sample was immersed in a solution prepared by dissolving Nafion in ethanol to have a concentration of 5 wt. %. Thereafter, a carbon paper as a sheet-shaped base material was stacked on the PtRu layer as a second catalyst layer and heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and an anode was manufactured on the Nafion 117.
  • a Pt layer was formed on the surface opposite to the surface formed with the anode in the Nafion 117 by the sputtering method, and the carbon paper was stacked on the Pt layer and pressure-bonded. Consequently, a cathode was manufactured on the Nafion 117, and a membrane electrode assembly was manufactured.
  • a carbon fiber layer with a diameter of several nm to several ten nm was grown as a first intermediate layer on a substrate formed of carbon by a low pressure CVD method.
  • PtRu was sputtered on the carbon fiber layer under a condition similar to the example 3 to form a PtRu layer with a thickness of 200 nm as a first catalyst layer.
  • the PtRu layer formed on the carbon fiber layer was constituted of PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • the Nafion 117 as a proton-conducting membrane was stacked on the PtRu layer so as to be in contact with the PtRu layer and heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and thereafter, only a substrate was peeled from the sample.
  • the sample in which a carbon fiber layer was exposed by peeling only the substrate was immersed in a Nafion solution of 2 wt. % and then dried at a room temperature.
  • a PtRu layer with a thickness of 200 nm was formed as a second catalyst layer on the carbon fiber layer by a sputtering method.
  • the PtRu layer as the second catalyst layer formed on the carbon fiber layer was constituted of the PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • the sample was immersed in a solution prepared by dissolving Nafion in ethanol to have a concentration of 5 wt. %. Thereafter, a carbon paper as a sheet-shaped base material was stacked on the PtRu layer as the second catalyst layer and heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and an anode was manufactured on the Nafion 117.
  • a Pt layer was formed on the surface opposite to the surface formed with the anode in the Nafion 117 by the sputtering method, and the carbon paper was stacked on the Pt layer and pressure-bonded. Consequently, a cathode was manufactured on the Nafion 117, and a membrane electrode assembly was manufactured.
  • a carbon fiber layer with a diameter of several nm to several ten nm was grown as a first intermediate layer on a substrate formed of carbon by a low pressure CVD method as in the example 4.
  • a PtRu layer with a thickness of 200 nm as a first catalyst layer was formed on the carbon fiber layer by a sputtering method.
  • the PtRu layer formed on the carbon fiber layer was constituted of PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • the Nafion 117 as a proton-conducting membrane was stacked on the PtRu layer and heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and then only a substrate was peeled from a sample. Subsequently, the sample in which a carbon fiber layer was exposed by peeling only the substrate was immersed in a Nafion solution of 2 wt. % as in the example 3 and then dried at a room temperature.
  • PtRu was sputtered on a carbon paper as a sheet-shaped base material under a condition similar to the example 3 to form a PtRu layer with a thickness of 200 nm as a second catalyst layer.
  • the PtRu layer as the second catalyst layer formed under such a condition was constituted of PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • the sample formed with the PtRu layer on the carbon paper was immersed in a Nafion solution of 2 wt. % and then dried at a room temperature.
  • the sample having the carbon paper was stacked on the sample having the Nafion 117 pressure-bonded in advance so that the PtRu layer as the second catalyst layer was in contact with the carbon fiber layer, and the laminate was heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and an anode was manufactured on the Nafion 117.
  • a Pt layer was formed on the surface opposite to the surface formed with the anode in the Nafion 117 by the sputtering method, and the carbon paper was stacked on the Pt layer and pressure-bonded. Consequently, a cathode was manufactured on the Nafion 117, and a membrane electrode assembly was manufactured.
  • a carbon fiber layer with a diameter of several nm to several ten nm was grown as a first intermediate layer on a substrate formed of carbon by a CVD method as in the example 4.
  • a PtRu layer with a thickness of 200 nm was formed as a first catalyst layer on the carbon fiber layer by a sputtering method.
  • the PtRu layer formed on the carbon fiber layer was constituted of the PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • the Nafion 117 as a proton-conducting membrane was stacked on the PtRu layer and heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and thereafter, only a substrate was peeled from the sample.
  • the sample in which the carbon fiber layer was exposed by peeling only the substrate was immersed in a Nafion solution of 2 wt. % and then dried at a room temperature. After that, a slurry prepared by mixing a Nafion solution of 10 wt. % and a carbon fiber powder was coated on the carbon fiber layer to be dried, and, thus, to form an intermediate layer as a second intermediate layer with a thickness of about 10 ⁇ m.
  • PtRu was sputtered on a carbon paper as a sheet-shaped base material under a similar condition as the example 3 to form a PtRu layer with a thickness of 200 nm as a second catalyst layer.
  • the PtRu layer as the second catalyst layer formed under such a condition was constituted of the PtRu particles having an average particle diameter of 0.1 to 2 ⁇ m.
  • the sample formed with the PtRu layer on the carbon paper was immersed in a Nafion solution of 2 wt. % and then dried at a room temperature.
  • the sample having the carbon paper was stacked on the sample having the Nafion 117 pressure-bonded in advance so that the PtRu layer as the second catalyst layer was in contact with the intermediate layer as the second intermediate layer.
  • the laminate was heated and pressure-bonded at 125° C. and a pressure of 30 kg/cm 2 for 10 minutes, and an anode was manufactured on the Nafion 117.
  • a Pt layer was formed on the surface opposite to the surface formed with the anode in the Nafion 117 by the sputtering method, and the carbon paper was stacked on the Pt layer and pressure-bonded. Consequently, a cathode was manufactured on the Nafion 117, and a membrane electrode assembly was manufactured.
  • single cells of a fuel direct supply type polyelectrolyte type fuel cell were manufactured using the membrane electrode assembly manufactured in the examples 1 to 6 and a separator.
  • a 1M aqueous methanol solution as a fuel was supplied to an anode at the flow rate of 0.6 ml/min, and, at the same time, air was supplied to a cathode at the flow rate of 200 ml/min.
  • discharge was performed so as to maintain a current density of 150 mA/cm 2 in such a state that those cells were maintained at 65° C. and the cell voltage after 30 minutes was measured, the voltage of 0.5 V was obtained in all the cells.
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